US5756565A - Non-gellable bitumen/polymer compositions - Google Patents

Non-gellable bitumen/polymer compositions Download PDF

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US5756565A
US5756565A US08/525,602 US52560295A US5756565A US 5756565 A US5756565 A US 5756565A US 52560295 A US52560295 A US 52560295A US 5756565 A US5756565 A US 5756565A
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bitumen
sulphur
adjuvant
process according
mixture
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Laurent Germanaud
Jean-Pascal Planche
Trung Kiet Phung
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Elf Antar France
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Elf Antar France
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D195/00—Coating compositions based on bituminous materials, e.g. asphalt, tar, pitch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch

Definitions

  • the invention relates to non-gellable bitumen/polymer compositions which are stable on storage at high temperature, that is to say, according to the invention, up to temperatures which may reach values of the order of 260° C.
  • the invention also relates to a process for the preparation of such compositions and equally concerns the application of these compositions to the production of bitumen/polymer binders which may be used to make coatings and especially road coatings.
  • bitumen/polymer compositions which possess enhanced stability and excellent physico-mechanical characteristics and which may be used to make various coatings, especially road surfacings, mixes or alternatively leaktight coatings, having enhanced characteristics compared with the coatings obtained from bitumens alone.
  • bitumen/polymer compositions of the abovementioned type for which the elastomer which is crosslinkable with sulphur is a copolymer of styrene and a conjugated diene, is described in particular in the citations FR-A-2,376,188, (U.S. Pat. No. 4,145,322), FR-A-2,528,439, (U.S. Pat. No. 4,554,313), and EP-A-0,360,656 (U.S. Pat. No. 5,508,112).
  • bitumen/polymer compositions of the abovementioned type from which bitumen/polymer binders are produced for making coatings, especially road coatings, are prepared in practice at polymer contents below a threshold which may range from about 3% to 6% by weight of bitumen depending on the nature and the molecular weight of the polymer, on the one hand, and the quality of the bitumen, on the other hand, gelling of the bitumen/polymer composition which is observed fairly frequently during the preparation of the said composition or while it is stored, occurs as soon as the polymer content of this composition exceeds the abovementioned threshold.
  • a threshold which may range from about 3% to 6% by weight of bitumen depending on the nature and the molecular weight of the polymer, on the one hand, and the quality of the bitumen, on the other hand, gelling of the bitumen/polymer composition which is observed fairly frequently during the preparation of the said composition or while it is stored, occurs as soon as the polymer content of this composition exceeds the above
  • bitumen/polymer compositions with a high polymer content which would act as bitumen/polymer concentrates, and are more economical to prepare and to transport than bitumen/polymer compositions with a lower polymer content, and which could be diluted at the time of use, by addition of bitumen, in order to obtain the corresponding bitumen/polymer binders with a lower polymer content which are usually used to make coatings.
  • bitumen/polymer compositions according to the invention are of the type consisting of a homogeneous mass formed of a bituminous matrix consisting of a bitumen or of a mixture of bitumens and in which is uniformly distributed an elastomer crosslinked with sulphur, in an amount between 3% and 30% and preferably between 5% and 25% of the weight of the bituminous matrix, and they are characterized in that an adjuvant, acting especially as an anti-gelling agent, is also present in the bituminous matrix in an amount between 0.1% and 5% and preferably between 0.2% and 3% of the weight of the said matrix, the said adjuvant consisting of one or more compounds of formula R--X, in which R is a monovalent C 2 to C 50 and more especially C 2 to C 40 organic radical and X denotes a functional group chosen from ##STR1## wherein Y representing a hydrogen atom or a radical R.
  • a process for the preparation of the bitumen/polymer compositions according to the invention is of the type in which, working at temperatures between 100° C. and 230° C. and with stirring for a period of at least 10 minutes, the bitumen or the mixture of bitumens chosen to constitute the bituminous matrix is placed in contact with, based on the weight of the bituminous matrix, between 3% and 30% and preferably between 5% and 25% of an elastomer which is crosslinkable with sulphur and a sulphur-donating coupling agent in an amount able to give an amount of free sulphur representing 0.1% to 20% and preferably 0.5% to 10% of the weight of the polymer which is crosslinkable with sulphur in the reaction medium formed of the coupling agent, elastomer and bituminous matrix ingredients, and it is characterized in that, during the said placing in contact, the reaction medium contains an adjuvant which acts in particular as an anti-gelling agent, the said adjuvant being used in an amount between 0.1% and
  • bitumen or mixture of bitumens which is placed in contact with the elastomer which is cross-linkable with sulphur, the anti-gelling adjuvant and the sulphur-donating coupling agent and which constitutes the bituminous matrix of the bitumen/polymer composition, is advantageously chosen from the various bitumens which possess a kinematic viscosity at 100° C. of between 0.5 ⁇ 10 -4 m 2 /s and 3 ⁇ 10 -2 ml/s and preferably between 1 ⁇ 10 -4 m 2 /s and 2 ⁇ 10 -2 m 2 /s.
  • bitumens may be bitumens from direct distillation or from distillation under reduced pressure or alternatively blown or semi-blown bitumens, or even certain petroleum fractions or mixtures of bitumens and distillates under vacuum.
  • bitumen or mixture of bitumens used to produce the compositions according to the invention has a penetrability, defined according to standard NF T 66004, of between 5 and 500 and preferably of between 20 and 400.
  • the elastomer which is crosslinkable with sulphur which is used to prepare the bitumen/polymer compositions and which is found crosslinked in the said compositions, may be such as polyisoprene, polynorbornene, polybutadiene, butyl rubber or ethylene/propylene/diene terpolymer (EPDM).
  • EPDM ethylene/propylene/diene terpolymer
  • the said elastomer is advantageously chosen from random or block copolymers of styrene and a conjugated diene such as butadiene, isoprene, chloroprene, carboxylated butadiene and carboxylated isoprene, and more particular consists of one or more copolymers chosen from block copolymers, with or without a random joint, of styrene and butadiene, of styrene and isoprene, of styrene and chloroprene, of styrene and carboxylated butadiene, or alternatively of styrene and carboxylated isoprene.
  • a conjugated diene such as butadiene, isoprene, chloroprene, carboxylated butadiene and carboxylated isoprene
  • the copolymer of styrene and conjugated diene advantageously possesses a weight content of styrene ranging from 5% to 50%.
  • the mean viscometric molecular weight of the copolymer of styrene and conjugated diene, and especially that of the copolymers mentioned above, may be between, for example, 10,000 and 600,000 and is preferably between 30,000 and 400,000.
  • the copolymer of styrene and conjugated diene is preferably chosen from the di- or triblock copolymers of styrene and butadiene, of styrene and isoprene, of styrene and carboxylated butadiene or alternatively of styrene and carboxylated isoprene which have styrene contents and viscometric molecular weights within the ranges defined above.
  • R advantageously represents a saturated or unsaturated C 2 to C 50 and more especially C 2 to C 40 monovalent hydrocarbon radical, the said radical being in particular of the linear or branched alkyl or alkenyl type, for example nonyl, dodecyl, tetradecyl, hexadecyl, octadecyl, octadecenyl, nonadecyl, eicosenyl, docosenyl or tetraco-senyl, of the alkylaryl type, for example nonylphenyl, dodecylphenyl, didodecylphenyl, tetradecylphenyl, dodecyltolyl, nonyltolyl, nonylxylyl, dodecylxylyl, dodecylcumenyl or hexadecylphenyl,
  • Non-limiting examples of anti-gelling adjuvants of formula R--X comprise carboxylic acids containing a saturated or unsaturated fatty chain, such as pelargonic acid, lauric acid, palmitic acid, stearic acid, myristic acid, behenic acid, oleic acid, erucic acid, linoleic acid and linolenic acid, alkylarenesulphonic acids bearing one or two saturated or unsaturated fatty chains on the ring, such as nonylbenzenesulphonic acid, dodecylbenzenesulphonic acid, didodecylbenzene-sulphonic acid, nonyltoluenesulphonic acid, nonylxylene-sulphonic acid, dodecyltoluenesulphonic acid and hexa-decylbenzenesulphonic acid, polycyclic acids containing condensed rings, such as abietic acid and the resinous acids derived from abietic acid, the mono
  • the sulphur-donating coupling agent which is used in the preparation of the bitumen/polymer compositions according to the invention, may consist of a product chosen from the group formed by elemental sulphur, hydrocarbyl polysulphides, sulphur-donating vulcanization accelerators and mixtures of such products with each other and/or with non-sulphur-donating vulcanization accelerators.
  • the sulphur-donating coupling agent is chosen from the products M which include, by weight, from 0% to 100% of a component A consisting of one or more sulphur-donating vulcanization accelerators and from 100% to 0% of a component B consisting of one or more vulcanization agents chosen from elemental sulphur and hydrocarbyl polysulphides, and the products N, which include a component C consisting of one or more non-sulphur-donating vulcanization accelerators and a product M in a weight ratio of the component C to the product M ranging from 0.01 to 1 and preferably from 0.05 to 0.5.
  • the elemental sulphur which may be used to constitute, in part or in total, the coupling agent is advantageously flowers of sulphur and preferably sulphur crystallized in the orthorhombic form and known under the name alpha sulphur.
  • the hydrocarbyl polysulphides which may be used to form a part or all of the coupling agent may be chosen from those which are defined in the citation FR-A-2,528,439 and which correspond to the general formula ##STR3## in which R 1 and R 2 each denote a saturated or unsaturated C 1 to C 20 monovalent hydrocarbon radical or are joined together to constitute a saturated or unsaturated C 1 to C 20 divalent hydrocarbon radical, forming a ring with the other associated groups of atoms in the formula, R 5 is a saturated or unsaturated C 1 to C 20 divalent hydrocarbon radical, the--(S)m--groups representing divalent groups each formed of m sulphur atoms, it being possible for m to be different from one of the said groups to another and denoting integers ranging from 1 to 6 with at least one m being equal to or greater than 2, and x represents an integer taking values from 0 to 10.
  • Preferred poly-sulphides correspond to the formula R 3 --(S)p--R 3 , in which R 3 denotes a C 6 to C 16 alkyl radical, for example hexyl, octyl, dodecyl, tert-dodecyl, hexadecyl, nonyl and decyl, and--(S) p--represents a divalent group formed by a chain of p sulphur atoms, p being an integer ranging from 2 to 5.
  • this accelerator may be chosen in particular from the thiuram polysulphides of formula ##STR4## in which the groups R 4 , which may be identical or different, each represent a C 1 to C 12 and preferably a C 1 to C 8 hydrocarbon radical, especially an alkyl, cycloalkyl or aryl radical, or alternatively two radicals R 4 attached to the same nitrogen atom are linked together to form a divalent C 2 to C 8 hydrocarbon radical and u is a number ranging from 2 to 8.
  • vulcanization accelerators which may especially be mentioned are the compounds dipentamethylenethiuram disulphide, dipenta-methylenethiuram tetrasulphide, dipentamethylenethiuram hexasulphide, tetrabutylthiuram disulphide, tetraethyl-thiuram disulphide and tetramethylthiuram disulphide.
  • sulphur-donating vulcanization accelerators which may also be mentioned are alkylphenol disulphides, and disulphides such as morpholine disulphide and caprolactam N,N'-disulphide.
  • the non-sulphur-donating vulcanization accelerators which may be used to form the component C of the coupling agents of product N type may be sulphur-containing compounds chosen especially from mercaptobenzothiazole and derivatives thereof, in particular metal benzothiazole thiolates and especially benzothiazolesulphenamides, dithiocarbamates of formula ##STR5## in which the groups R 4 , which may be identical or different, have the meaning given above, Y represents a metal and v denotes the valence of Y, and thiuram monosulphides of formula ##STR6## in which groups R 4 have the meaning given above.
  • vulcanization accelerators of the mercaptobenzothiazole type may be such as mercaptobenzothiazole, benzothiazole thiolate of a metal such as zinc, sodium or copper, benzothiazyl disulphide, 2-benzothiazolepentamethylenesulphenamide, 2-benzothiazolethiosulphenamide, 2-benzothiazoledihydrocarbylsulphenamides for which the hydrocarbon radical is an ethyl, isopropyl, tert-butyl or cyclohexyl radical, and N-oxydiethylene-2-benzothiazolesulphenamide.
  • vulcanization accelerators of the dithiocarbamate type of abovementioned formula there may be mentioned the compounds: dimethyldithiocarbamates of metals such as copper, zinc, lead, bismuth and selenium, diethyldithiocarbamates of metals such as cadmium and zinc, diamyldithiocarbamates of metals such as cadmium, zinc and lead, and lead or zinc pentamethylenedithiocarbamate.
  • thiuram monosulphides having the formula given above there may be mentioned compounds such as dipentamethylenethiuram monosulphide, tetramethylthiuram monosulphide, tetraethylthiurammonosulphide and tetrabutylthiuram monosulphide.
  • vulcanization accelerators which do not belong to the families defined above, may also be used.
  • vulcanization accelerators may be such as 1,3-diphenylguanidine, di-ortho-tolylguanidine and zinc oxide.
  • the coupling agent may be of the monocomponent type or of the multicomponent type, it being possible for the coupling agent of the multicomponent type to be formed prior to its use or alternatively produced in situ in the medium in which it needs to be present.
  • the coupling agent of the preformed multicomponent type or of the monocomponent type or the components of the coupling agents of the multicomponent type formed in situ may be used as they are, for example in the molten state, or alternatively as a mixture, for example in solution or in suspension, with a diluent, for example a hydrocarbon compound.
  • the process for the preparation of the bitumen/polymer compositions according to the invention is advantageously carried out by first placing the elastomer which is crosslinkable with sulphur and the adjuvant of formula R--X in contact with the bitumen or the mixture of bitumens intended to form the bituminous matrix of the compositions, using proportions of elastomer and of adjuvant having values, relative to the bituminous matrix, chosen within the ranges defined above for these proportions, working at temperatures between 100° C. and 230° C., more particularly between 120° C.
  • the adjuvant may be incorporated into the bitumen or bitumen mixtures before or after the elastomer, it being equally possible to envisage a simultaneous incorporation.
  • the adjuvant is incorporated into the bitumen or mixture of bitumens before the elastomer.
  • bitumen/polymer compositions according to the invention may also include various additives and especially promoters of adhesion of the final bitumen/polymer binder to mineral surfaces.
  • the said additives may be added to the reaction medium formed of the bitumen or mixture of bitumens, the elastomer which is crosslinkable with sulphur, the adjuvant of formula R--X and the coupling agent, at any particular moment in the formation of the said reaction medium and preferably before addition of the coupling agent to a medium consisting of the other ingredients.
  • bitumen/polymer compositions according to the invention are non-gellable and stable on storage up to high temperatures which may reach values of the order of 260° C. They may be used as they are or else diluted with variable proportions of a bitumen or of a mixture of bitumens in order to constitute bitumen/polymer binders having a chosen content of crosslinked elastomer, which may either be equal to (non-diluted composition) or else less than (diluted composition) the content of cross-linked elastomer in the corresponding initial bitumen/polymer compositions.
  • bitumen/polymer compositions may be diluted with the bitumen or mixture of bitumens either directly after the said compositions have been obtained, when an almost immediate use of the resulting bitumen/polymer binders is required, or alternatively after a longer or shorter period of storage of the bitumen/polymer compositions, when a delayed use of the resulting bitumen/polymer binders is envisaged.
  • the bitumen or mixture of bitumens used to dilute a bitumen/polymer composition according to the invention may be chosen from the bitumens defined above as being suitable for the preparation of the bitumen/polymer compositions.
  • bitumen/polymer composition according to the invention with a bitumen or a mixture of bitumens in order to form a bitumen/polymer binder having a chosen content of crosslinked elastomer, which is less than that of the bitumen/polymer composition, is generally performed by bringing together, with stirring and at temperatures between 100° C. and 230° C. and more particularly between 120° C. and 190° C., suitable proportions of the bitumen/polymer composition and of bitumen or mixture of bitumens.
  • the amount of dilution bitumen or mixture of bitumens may be chosen so that the bitumen/polymer binder resulting from the dilution of the bitumen/polymer composition includes, by weight of the bituminous matrix, between 0.5% and 5% of crosslinked elastomer.
  • bitumen/polymer binders consisting of the bitumen/polymer compositions according to the invention or resulting from the dilution of the said compositions with a bitumen or mixture of bitumens, to the desired content of crosslinked elastomer in the said binders, may be applied, directly or after placing in aqueous emulsion, to the production of road coatings of the surface coating type, to the production of mixes laid under hot or cold conditions, or alternatively to the production of leaktight coatings.
  • a non-gelled bitumen/polymer composition (product II) was obtained, having the penetrability and ring and ball softening point values given in Table I compared with those for the pure bitumen (product I.a) and with those for the control bitumen/polymer composition of Example 1 (product I.b).
  • pelargonic acid anti-gelling adjuvant according to the invention
  • a non-gelled bitumen/polymer composition with a high polymer content (6% by weight) having a markedly improved ring and ball softening point.
  • the corresponding control composition prepared in the absence of pelargonic acid or other adjuvant according to the invention is gelled and impossible to handle.
  • bitumen/polymer compositions according to the invention by changing the nature of the anti-gelling adjuvant
  • Example 2 The process was performed as described in Example 2, except that the nature of the anti-gelling adjuvant is changed from one example to the next, the other operating conditions being those of Example 2.
  • Example 6 mixture of linear C 16 to C 18 fatty acids and natural resinous acids having the following characteristics:
  • Example 7 mixture of linear natural fatty acids and resinous acids having the following characteristics:
  • Example 8 distillation residue of a mixture of acids having the following characteristics:
  • the penetrability and RBSP (ring and ball softening point) values of the "Products Z.a” (bitumen/polymer compositions) and the penetrability and RBSP values and the rheological characteristics in traction (according to standard NF T 46 002) of the "Products Z.b” (bitumen/polymer binders obtained by dilution of the compositions) are collated in Table II.
  • control bitumen/polymer composition (product I.b), prepared in the absence of adjuvant according to the invention, is gelled and impossible to handle.
  • a non-gelled bitumen/polymer composition (product IX.a) including about 9% by weight of styrene/butadiene copolymer was obtained.
  • Table III below gives the penetrability and RBSP values of the composition thus obtained, measured during storage of the said composition at high temperature (about 163° C.).
  • bitumen/polymer composition obtained above (product IX.a) a bitumen/polymer binder (product IX.b) containing 3% styrene/butadiene copolymer was prepared. To do this, 100 parts of the said composition, withdrawn 120 minutes after introduction of the sulphur, were mixed with 200 parts of the pure starting bitumen, the mixing operation being performed with stirring at 185° C. for 90 minutes.
  • Table IV gives the penetrability and RBSP values as well as the traction properties of the bitumen/polymer binder (product IX.b) obtained.
  • the process was performed as described in Example 9, except that the adjuvant was replaced by the same amount of a xylenesulphonic acid bearing a linear C 16 to C18 fatty alkyl radical on the ring, the said acid having a molar mass of 430.
  • a non-gelled bitumen/polymer composition (product X.a) including about 9% styrene/butadiene copolymer was obtained.
  • Table V gives the penetrability and RBSP values for the composition thus obtained, measured during storage of the said composition at high temperature (about 163° C.) for several days.
  • a non-gelled bitumen/polymer composition including about 8% by weight of styrene/butadiene crosslinked copolymer was obtained.
  • Table VI gives the penetrability and RBSP values for the composition thus obtained, measured during storage of the said composition at high temperature, namely about 160° C.
  • Example 9 The process was performed as described in Example 9, except that the adjuvant of Example 9 was replaced by the same amount of an equimolar mixture of mono- and diethylphosphoric acids.
  • a non-gelled bitumen/polymer composition having a dynamic viscosity at 140° C. equal to 21 Poises and including about 9% of crosslinked styrene/butadiene diblock copolymer (product XII.a) was thus obtained.
  • Table VII below gives the penetrability and RBSP values for the said composition thus obtained, measured during storage of this composition at high temperature, namely about 163° C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Sealing Material Composition (AREA)
US08/525,602 1992-03-26 1994-03-24 Non-gellable bitumen/polymer compositions Expired - Fee Related US5756565A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9303492 1993-03-26
FR9303492A FR2703063A1 (fr) 1993-03-26 1993-03-26 Compositions bitume/polymère non gélifiables et stables au stockage à température élevée, leur procédé de préparation et leur application à la production de liants bitume/polymère pour revêtements.
PCT/FR1994/000323 WO1994022958A1 (fr) 1993-03-26 1994-03-24 Compositions bitume/polymere non gelifiables

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US (1) US5756565A (de)
EP (1) EP0690892B1 (de)
JP (1) JP3583425B2 (de)
AT (1) ATE153364T1 (de)
BR (1) BR9406167A (de)
CA (1) CA2158346C (de)
DE (1) DE69403330T2 (de)
DK (1) DK0690892T3 (de)
ES (1) ES2105671T3 (de)
FR (1) FR2703063A1 (de)
NO (1) NO308219B1 (de)
WO (1) WO1994022958A1 (de)

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6011095A (en) * 1996-05-10 2000-01-04 Elf Antar France Method for preparing bitumen/polymer compositions and use thereof
US6180697B1 (en) 1999-09-04 2001-01-30 Fina Technology, Inc. Method for preparation of stable bitumen polymer compositions
US6310122B1 (en) 1999-09-03 2001-10-30 Fina Technology, Inc. Stable bitumen polymer compositions
US6407152B1 (en) 2000-11-28 2002-06-18 Fina Technology, Inc. Method for preparing asphalt and polymer compositions incorporating multi-component crosslinking agents
US6441065B1 (en) 1999-09-03 2002-08-27 Fina Technology, Inc. Method for preparation of stable bitumen polymer compositions
US6469075B1 (en) 1999-09-04 2002-10-22 Fina Technology, Inc. Method and preparation of stable bitumen polymer compositions
US6569351B1 (en) 2000-03-14 2003-05-27 Ergon, Inc. Accelerator-gel additive for use in the production of polymer-modified asphalt
WO2004055115A1 (en) * 2002-12-12 2004-07-01 Ram Technologies Group, Inc. Improved rubber modified asphalt cement compositions and methods
US6767939B2 (en) 1999-09-04 2004-07-27 Fina Technology, Inc. Method for preparation of stable bitumen polymer compositions
US20040225036A1 (en) * 2002-08-29 2004-11-11 Ram Technologies Group, Inc. Rubber modified asphalt cement compositions and methods
US20050101701A1 (en) * 2003-11-12 2005-05-12 Stuart Richard K.Jr. Modified asphalt compositions
US20050101702A1 (en) * 2003-11-12 2005-05-12 Stuart Richard K.Jr. Modified asphalt compositions
US20060074141A1 (en) * 2004-10-06 2006-04-06 Tri-E Shielding Technologies, Llc Techniques and compositions for shielding radioactive energy
US20070249762A1 (en) * 2002-08-29 2007-10-25 Ram Technologies Group, Inc. Rubber modified asphalt cement compositions and methods
US20070287778A1 (en) * 2006-05-31 2007-12-13 Jean-Valery Martin Method for preparing an improved bitumen by addition of polyphosphoric acid and a cross-linkable polymer
US20080242770A1 (en) * 2005-07-21 2008-10-02 Gordon William Thomas Process for preparing bitumen/asphalt bale
US20090105376A1 (en) * 2004-04-14 2009-04-23 Jan Korenstra Polymer modified bitumen composition to be used in asphalt binders or roofing compositions
CN100487056C (zh) * 2004-12-17 2009-05-13 同济大学 一种沥青抗剥落剂及其制备方法
WO2009128827A1 (en) 2008-04-17 2009-10-22 Kraton Polymers Us Llc A block copolymer and polymer modified bituminous binder compositon for use in base course asphalt paving application
US20100190894A1 (en) * 2007-07-24 2010-07-29 Total Raffinage Marketing Graft polymer and thermoreversibly cross-linked bitumen composition comprising said graft polymer
US20100192804A1 (en) * 2007-01-23 2010-08-05 Total Raffinage Marketing Bituminous composition with thermoreversible properties
US20100197835A1 (en) * 2007-07-24 2010-08-05 Total Reffinage Marketing Thermoreversibly crosslinked bitumen/polymer composition
US20110098385A1 (en) * 2008-04-08 2011-04-28 Total Raffinage Marketing Process for cross-linking bitumen/polymer compositions having reduced emissions of hydrogen sulphide
US20110144242A1 (en) * 2007-11-27 2011-06-16 Total Raffinage Marketing Thermoreversibly crosslinked elastic bituminous composition
US10131788B2 (en) 2012-07-02 2018-11-20 Total Marketing Services Bituminous compositions comprising additives having improved thermoreversible properties

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2739863B1 (fr) * 1995-10-16 1997-11-21 Elf Antar France Procede de preparation de compositions bitume/polymere a caractere multigrade renforce et application des compositions obtenues a la production de liants bitume/polymere pour revetements
FR2740138B1 (fr) * 1995-10-19 1997-11-21 Elf Aquitaine Elastomere fonctionnalise par des groupements carboxyliques ou esters greffes et son application a la production de compositions bitume/elastomere fonctionnalise utilisables pour la realisation de revetements
JP3313297B2 (ja) * 1997-01-30 2002-08-12 日本エラストマー株式会社 新規アスファルト組成物、及び新規アスファルト改質用ブロック共重合体組成物
FR2805822B1 (fr) * 2000-03-01 2005-05-06 Elf Antar France Procede de preparation de compositions bitume/polymere reticulees, leur application a la production de liants bitume/polymere pour revetements et solution mere de polymere pour leur obtention
JP5424704B2 (ja) * 2009-05-01 2014-02-26 昭和シェル石油株式会社 スチレン−ブタジエン系組成物
JP5571357B2 (ja) * 2009-11-06 2014-08-13 昭和シェル石油株式会社 アスファルト組成物
FR2984329B1 (fr) 2011-12-20 2014-11-21 Total Raffinage Marketing Polymere greffe et composition bitume/polymere a reticulation thermoreversible contenant un tel polymere
FR2992654B1 (fr) 2012-07-02 2015-08-07 Total Raffinage Marketing Compositions bitumineuses additivees aux proprietes thermoreversibles ameliorees

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4882373A (en) * 1987-07-24 1989-11-21 Exxon Research And Engineering Company Asphaltic composition
US5070123A (en) * 1988-08-29 1991-12-03 Exxon Research & Engineering Company Method for improving the storage stability of polymer modified asphalt
US5078905A (en) * 1987-07-02 1992-01-07 Societe Anonyme D'application Des Derives De L'asphalte Binders for road-making comprising benzothiazole compounds and dithiomorpholine
US5095055A (en) * 1989-08-23 1992-03-10 Exxon Research And Engineering Company Using branched polymers to improve the storage stability of acid treated polymer modified asphalts (PNE-577)
US5120777A (en) * 1989-06-30 1992-06-09 Elf France Bitumen/polymer composition exhibiting an adhesiveness which is retained on storage at elevated temperature and process for preparing such a composition
US5225462A (en) * 1991-01-24 1993-07-06 Euron S.P.A. Bitumen-polymer mixtures and a process for their preparation
US5508112A (en) * 1988-09-09 1996-04-16 Elf France Process for the preparation of bitumen-polymer composition

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1969904A (en) * 1931-11-06 1934-08-14 Charles J Hepburn Bituminous road making composition
BE436599A (de) * 1938-10-07
US2693425A (en) * 1952-04-14 1954-11-02 Standard Oil Co Asphalt cement of improved wetting properties
JPS4960322A (de) * 1972-10-18 1974-06-12
JPH0832832B2 (ja) * 1984-03-09 1996-03-29 花王株式会社 加熱瀝青質用添加剤
US4647313A (en) * 1985-10-17 1987-03-03 Exxon Research And Engineering Company Paving asphalt
FR2636340B1 (fr) * 1988-09-09 1992-04-17 Elf France Procede de preparation de compositions bitume-polymere, application des compositions obtenues a la realisation de revetements et solution mere de polymere utilisable pour l'obtention desdites compositions

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5078905A (en) * 1987-07-02 1992-01-07 Societe Anonyme D'application Des Derives De L'asphalte Binders for road-making comprising benzothiazole compounds and dithiomorpholine
US4882373A (en) * 1987-07-24 1989-11-21 Exxon Research And Engineering Company Asphaltic composition
US5070123A (en) * 1988-08-29 1991-12-03 Exxon Research & Engineering Company Method for improving the storage stability of polymer modified asphalt
US5508112A (en) * 1988-09-09 1996-04-16 Elf France Process for the preparation of bitumen-polymer composition
US5120777A (en) * 1989-06-30 1992-06-09 Elf France Bitumen/polymer composition exhibiting an adhesiveness which is retained on storage at elevated temperature and process for preparing such a composition
US5095055A (en) * 1989-08-23 1992-03-10 Exxon Research And Engineering Company Using branched polymers to improve the storage stability of acid treated polymer modified asphalts (PNE-577)
US5225462A (en) * 1991-01-24 1993-07-06 Euron S.P.A. Bitumen-polymer mixtures and a process for their preparation

Cited By (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6011095A (en) * 1996-05-10 2000-01-04 Elf Antar France Method for preparing bitumen/polymer compositions and use thereof
US6310122B1 (en) 1999-09-03 2001-10-30 Fina Technology, Inc. Stable bitumen polymer compositions
US6441065B1 (en) 1999-09-03 2002-08-27 Fina Technology, Inc. Method for preparation of stable bitumen polymer compositions
US6767939B2 (en) 1999-09-04 2004-07-27 Fina Technology, Inc. Method for preparation of stable bitumen polymer compositions
US6180697B1 (en) 1999-09-04 2001-01-30 Fina Technology, Inc. Method for preparation of stable bitumen polymer compositions
US7186765B2 (en) 1999-09-04 2007-03-06 Fina Technology, Inc. Method for preparation of stable bitumen polymer compositions
US6469075B1 (en) 1999-09-04 2002-10-22 Fina Technology, Inc. Method and preparation of stable bitumen polymer compositions
US20050038142A1 (en) * 1999-09-04 2005-02-17 Butler James R. Method for preparation of stable bitumen polymer compositions
US6569351B1 (en) 2000-03-14 2003-05-27 Ergon, Inc. Accelerator-gel additive for use in the production of polymer-modified asphalt
US6569925B2 (en) 2000-03-14 2003-05-27 Ergon, Incorporated Accelerator-gel additive for use in the production of polymer modified asphalt
US6407152B1 (en) 2000-11-28 2002-06-18 Fina Technology, Inc. Method for preparing asphalt and polymer compositions incorporating multi-component crosslinking agents
US20040225036A1 (en) * 2002-08-29 2004-11-11 Ram Technologies Group, Inc. Rubber modified asphalt cement compositions and methods
US7074846B2 (en) 2002-08-29 2006-07-11 Ram Technologies, Inc. Rubber modified asphalt cement compositions and methods
US20070249762A1 (en) * 2002-08-29 2007-10-25 Ram Technologies Group, Inc. Rubber modified asphalt cement compositions and methods
WO2004055115A1 (en) * 2002-12-12 2004-07-01 Ram Technologies Group, Inc. Improved rubber modified asphalt cement compositions and methods
US7439286B2 (en) 2003-11-12 2008-10-21 Westlake Longview Corporation Modified asphalt compositions
USRE41167E1 (en) * 2003-11-12 2010-03-23 Westlake Longview Corporation Modified asphalt compositions
US7202290B2 (en) 2003-11-12 2007-04-10 Eastman Chemical Company Modified asphalt compositions
US20050101702A1 (en) * 2003-11-12 2005-05-12 Stuart Richard K.Jr. Modified asphalt compositions
USRE42165E1 (en) * 2003-11-12 2011-02-22 Westlake Longview Corp. Modified asphalt compositions
US7144933B2 (en) 2003-11-12 2006-12-05 Eastman Chemical Company Modified asphalt compositions
US20050101701A1 (en) * 2003-11-12 2005-05-12 Stuart Richard K.Jr. Modified asphalt compositions
US20090105376A1 (en) * 2004-04-14 2009-04-23 Jan Korenstra Polymer modified bitumen composition to be used in asphalt binders or roofing compositions
US20060074141A1 (en) * 2004-10-06 2006-04-06 Tri-E Shielding Technologies, Llc Techniques and compositions for shielding radioactive energy
US7449131B2 (en) 2004-10-06 2008-11-11 Terry Industries, Inc. Techniques and compositions for shielding radioactive energy
US20090039318A1 (en) * 2004-10-06 2009-02-12 Tri-E Shielding Technologies, Llc. Techniques and compositions for shielding radioactive energy
US7553431B2 (en) 2004-10-06 2009-06-30 Terry Industries, Inc. Techniques and compositions for shielding radioactive energy
CN100487056C (zh) * 2004-12-17 2009-05-13 同济大学 一种沥青抗剥落剂及其制备方法
CN101024476B (zh) * 2005-07-21 2010-06-23 东方炼油公司 制备沥青包的方法及得到的产品
US20080242770A1 (en) * 2005-07-21 2008-10-02 Gordon William Thomas Process for preparing bitumen/asphalt bale
US7820743B2 (en) 2005-07-21 2010-10-26 Eastern Petroleum Sdn Bhd Process for preparing bitumen/asphalt bale
US20070287778A1 (en) * 2006-05-31 2007-12-13 Jean-Valery Martin Method for preparing an improved bitumen by addition of polyphosphoric acid and a cross-linkable polymer
US7985787B2 (en) 2006-05-31 2011-07-26 Jean-Valery Martin Method for preparing an improved bitumen by addition of polyphosphoric acid and a cross-linkable polymer
US9238752B2 (en) 2007-01-23 2016-01-19 Total Raffinage Marketing Bituminous composition with thermoreversible properties
US20100192804A1 (en) * 2007-01-23 2010-08-05 Total Raffinage Marketing Bituminous composition with thermoreversible properties
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US8722776B2 (en) 2007-07-24 2014-05-13 Total Marketing Services Graft polymer and thermoreversibly cross-linked bitumen composition comprising said graft polymer
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US20110144242A1 (en) * 2007-11-27 2011-06-16 Total Raffinage Marketing Thermoreversibly crosslinked elastic bituminous composition
US8506699B2 (en) 2007-11-27 2013-08-13 Total Raffinage Marketing Thermoreversibly crosslinked elastic bituminous composition
US20110098385A1 (en) * 2008-04-08 2011-04-28 Total Raffinage Marketing Process for cross-linking bitumen/polymer compositions having reduced emissions of hydrogen sulphide
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US20110034594A1 (en) * 2008-04-17 2011-02-10 Erik Jan Scholten Block copolymer and polymer modified bituminous binder composition for use in base course asphalt paving application
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US10131788B2 (en) 2012-07-02 2018-11-20 Total Marketing Services Bituminous compositions comprising additives having improved thermoreversible properties

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DE69403330T2 (de) 1998-01-02
ES2105671T3 (es) 1997-10-16
EP0690892B1 (de) 1997-05-21
NO953745L (no) 1995-09-22
DE69403330D1 (de) 1997-06-26
NO953745D0 (no) 1995-09-22
JPH08508310A (ja) 1996-09-03
ATE153364T1 (de) 1997-06-15
EP0690892A1 (de) 1996-01-10
DK0690892T3 (da) 1997-12-15
BR9406167A (pt) 1996-01-09
FR2703063A1 (fr) 1994-09-30
JP3583425B2 (ja) 2004-11-04
CA2158346A1 (fr) 1994-10-13
NO308219B1 (no) 2000-08-14
CA2158346C (fr) 2006-05-09
WO1994022958A1 (fr) 1994-10-13

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